WO2022105204A1 - High-solid-content low-voc protective coating, preparation method therefor and use thereof - Google Patents

High-solid-content low-voc protective coating, preparation method therefor and use thereof Download PDF

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Publication number
WO2022105204A1
WO2022105204A1 PCT/CN2021/099700 CN2021099700W WO2022105204A1 WO 2022105204 A1 WO2022105204 A1 WO 2022105204A1 CN 2021099700 W CN2021099700 W CN 2021099700W WO 2022105204 A1 WO2022105204 A1 WO 2022105204A1
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Prior art keywords
low
solid
protective coating
parts
viscosity
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PCT/CN2021/099700
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French (fr)
Chinese (zh)
Inventor
谢海
胡明
钱金均
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江苏冠军科技集团股份有限公司
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Publication of WO2022105204A1 publication Critical patent/WO2022105204A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

Definitions

  • the invention relates to the technical field of coatings, in particular to a high-solid low-VOC protective coating and a preparation method and application thereof.
  • Solvent-based coatings have high decorative, durable protection and versatility, and are widely used in modern industry, national defense, information, biochemistry, new materials, aerospace, marine development, renewable energy development, environmental protection and other fields.
  • Organic solvents in solvent-based coatings play a key role. For example, organic solvents can reduce the surface tension of coatings, improve the wetting and dispersing properties of pigments, adjust the viscosity of film formers and coatings, and improve the fluidity of coatings. Products meet different paint requirements and construction requirements.
  • the purpose of the present invention is to provide a high-solid low-VOC protective coating and a preparation method and application thereof.
  • the high-solid low-VOC protective coating provided by the present invention has good anti-rust effect, is convenient to construct and is more environmentally friendly.
  • the present invention provides a kind of high solid content low VOC protective coating, including the following components by weight:
  • Anti-skinning agent 0.2 to 0.3 parts.
  • the high-solid and low-viscosity alkyd resin is prepared from natural vegetable oil through high temperature reaction;
  • the temperature of the high-temperature reaction is 180-250° C., and the time is 7-11 h.
  • the addition of diethylene glycol butyl ether and/or diethylene glycol methyl ether solvent is also included to adjust the viscosity of the obtained resin.
  • the preferred natural vegetable oils include one or more of soybean oil, linseed oil and cottonseed oil.
  • the solid content of the high-solid and low-viscosity alkyd resin is 70 ⁇ 2% when baked at 105°C for 1 hour, and the viscosity at 25°C is 200-250s.
  • titanium dioxide is rutile type titanium dioxide with a particle size of 10-100 nm.
  • the particle size of the ground calcium carbonate is 1100-1300 mesh.
  • the alcohol ether solvent includes diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, diethylene glycol ethyl ether and tripropylene glycol methyl ether one or more of them.
  • the wetting agent is silicone oil; the dispersant includes a phosphate ester dispersant; the drier includes one or more of metal oxides, metal salts and rare earth driers;
  • the crusting agent is methyl ethyl ketoxime.
  • the metals in the metal oxides and metal salts independently include cobalt, manganese, iron, zinc or calcium;
  • the rare earth elements in the rare earth drier include one or more of cerium, lanthanum and yttrium .
  • the viscosity of the coating at 25°C is 190-210s.
  • the present invention provides the preparation method of the above-mentioned high solid content low VOC protective coating, comprises the following steps:
  • the slurry, the remaining high-solid and low-viscosity alkyd resin, the drier, the remaining alcohol ether solvent and the anti-skinning agent are mixed to obtain a protective coating.
  • the part of the alcohol ether solvent accounts for 75-85% of the total mass of the alcohol ether solvent
  • the part of the high-solid and low-viscosity alkyd resin accounts for 65-75% of the total mass of the high-solid and low-viscosity alkyd resin; the fineness of the slurry is less than or equal to 40 ⁇ m.
  • the mixing speed is 80-1000 rpm.
  • the present invention provides the application of the above-mentioned high-solid low-VOC protective coating in industrial anti-corrosion.
  • the industrial anticorrosion is steel structure protection.
  • the invention provides a preparation method of high-solid low-viscosity alkyd resin, comprising the following steps:
  • Natural vegetable oil is reacted at high temperature to prepare high solid and low viscosity alkyd resin
  • the temperature of the high-temperature reaction is 180-250° C., and the time is 7-11 h.
  • the addition of diethylene glycol butyl ether and/or diethylene glycol methyl ether solvent is also included to adjust the viscosity of the obtained resin.
  • the natural vegetable oil includes one or more of soybean oil, linseed oil and cottonseed oil.
  • the present invention takes high-solid and low-viscosity alkyd resin as the main body, and adds alcohol ether solvent, heavy calcium carbonate, organic bentonite, under the action of wetting agent, dispersant, drier and anti-skinning agent, the obtained
  • the protective coating has high solid content and is an environmentally friendly protective coating; good adhesion, flexibility, alkali resistance, acid resistance, abrasion resistance and weather resistance, and low toxicity, green environmental protection, and high hardness, smooth and delicate paint film, It is non-toxic, non-polluting, and can effectively extend the life of the high solids and low VOC protective coatings.
  • the invention provides the preparation method of the high-solid low-VOC protective coating, which is simple to operate and suitable for large-scale production.
  • the present invention provides a kind of high solid content low VOC protective coating, including the following components by weight:
  • Anti-skinning agent 0.2 to 0.3 parts.
  • the raw materials for preparing the high-solids and low-VOC protective coatings include 55-65 parts, preferably 60-65 parts, of high-solids and low-viscosity alkyd resins.
  • the high-solid and low-viscosity alkyd resin is preferably prepared from natural vegetable oil through high temperature reaction. In the present invention, during the high temperature reaction, the natural vegetable oil undergoes alcoholysis first, and then undergoes polymerization.
  • the natural vegetable oil preferably includes one or more of soybean oil, linseed oil and cottonseed oil, more preferably soybean oil, linseed oil or cottonseed oil.
  • the temperature of the high-temperature reaction is preferably 180-250°C, more preferably 190-220°C; the time of the high-temperature reaction is preferably 7-11 h, more preferably 8-10 h.
  • the present invention preferably further includes adding diethylene glycol butyl ether and/or diethylene glycol methyl ether solvent to adjust the viscosity of the obtained resin;
  • the content is preferably 70 ⁇ 2% (baking at 105°C for 1 h), and the viscosity is preferably 200-250s (coating-4 viscometer, 25°C).
  • the raw materials for preparing the protective coating include 8-15 parts of heavy calcium carbonate, preferably 8-13 parts.
  • the particle size of the ground calcium carbonate is preferably 1100-1300 mesh, more preferably 1200 mesh.
  • the heavy calcium carbonate is used as an extender pigment. Too much dosage will affect the film-forming effect of the steel structure protective paint, and too little dosage will affect the mechanical properties of the steel structure protective paint film.
  • the heavy calcium carbonate is used in combination with other raw materials, and the performance of the steel structure protective coating can be improved.
  • the raw materials for preparing the protective coating include 6-10 parts, preferably 7-9 parts, of alcohol ether solvents.
  • the alcohol ether solvent preferably includes diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, diethylene glycol ethyl ether and tripropylene glycol One or more of methyl ethers.
  • too much or too little amount of the alcohol ether solvent will affect the viscosity of the steel structure protective coating, and then affect its film-forming effect and performance.
  • the alcohol ether solvent is used in combination with other raw materials, so that the performance of the steel structure protective coating can be improved.
  • the raw materials for preparing the protective coating include 0.3-0.5 parts of organic bentonite, preferably 0.32-0.4 parts, more preferably 0.32 parts, 0.34 servings, 0.36 servings, 0.38 servings or 0.40 servings.
  • the function of the organobentonite is to prevent the precipitation of other raw materials; if the amount of the organobentonite is too large, the viscosity of the steel structure protective coating will be too large, and the amount of the organic bentonite will be too small, and the anti-settling effect will not be achieved.
  • the organic bentonite is used in combination with other raw materials, and the performance of the steel structure protective coating can be improved.
  • the raw materials for preparing the protective coating include 0.2-0.4 parts of wetting agent, preferably 0.22-0.4 parts, more preferably 0.25 parts , 0.3 servings, 0.35 servings or 0.40 servings.
  • the wetting agent of the present invention is preferably silicone oil.
  • the silicone oil can well wet the pigments and fillers, thereby helping to improve the grinding efficiency of titanium dioxide and heavy calcium carbonate and the coating of other raw materials by low-viscosity alkyd resin, preventing titanium dioxide, heavy Calcium carbonate and other raw materials float color; too much amount of the wetting agent will cause shrinkage of the steel structure protective paint film, and too little amount will cause the steel structure protective paint film to bloom.
  • the wetting agent is used in combination with other raw materials, and the performance of the protective coating for steel structures can be improved.
  • the raw materials for preparing the protective coating include 0.3-0.5 parts of dispersant, preferably 0.35-0.5 parts, more preferably 0.35 parts, 0.4 servings, 0.45 servings or 0.5 servings.
  • the dispersant preferably includes a phosphoric acid ester type dispersant, preferably a DisperBYK-110 or DisperBYK-111 type dispersant.
  • the function of the dispersant is to disperse pigments and fillers; if the amount of the dispersant is too much, the drying of the steel structure protective paint film will be slow, and if the amount is too small, the color of the steel structure protective paint film will float. , paint precipitation.
  • the dispersant is used in combination with other raw materials, and the performance of the protective coating for steel structures can be improved.
  • the raw materials for preparing the protective coating include 0.7-1 part, preferably 0.75-1 part, and more preferably 0.75 part of a drier. , 0.8 servings, 0.85 servings, 0.9 servings, 0.95 servings or 1 serving.
  • the drier includes one or more of metal oxides, metal salts and rare earth driers; the metals in the metal oxides and metal salts independently include cobalt, manganese, iron, Zinc or calcium.
  • the rare earth element in the rare earth drier includes one or more of cerium, lanthanum and yttrium.
  • the role of the drier is to speed up the drying of the steel structure protective paint film; the excessive amount of the drier will cause the steel structure protective paint to be easily crusted, and the excessive amount will lead to the steel structure protective paint.
  • the paint film is not easy to dry.
  • the drier is used in combination with other raw materials, and the performance of the steel structure protective coating can be improved.
  • the raw materials for preparing the protective coating include 0.2-0.3 parts of anti-skinning agent, preferably 0.22-0.3 parts, more preferably 0.22 parts serving, 0.24 serving, 0.26 serving, 0.28 serving, or 0.3 serving.
  • the anti-skinning agent of the present invention is preferably methyl ethyl ketoxime.
  • the role of the methyl ethyl ketoxime is to prevent the steel structure protective coating from crusting during storage; the excessive dosage of the anti-skinning agent will cause the steel structure protective coating paint film to not dry, and the dosage is too small to achieve Anti-skinning effect.
  • the anti-skinning agent is used in combination with other raw materials, and the performance of the steel structure protective coating can be improved.
  • the raw materials for preparing the protective coating include 15-20 parts of titanium dioxide, preferably 15-18 parts.
  • the titanium dioxide is used as a coloring pigment. Too much dosage will affect the production cost of the steel structure protective coating, and too little dosage will affect the hiding power of the steel structure protective coating.
  • the titanium dioxide is preferably a rutile type titanium dioxide, more preferably a chloride method rutile type titanium dioxide. In the invention, the titanium dioxide is used in combination with other raw materials, and the performance of the protective coating for steel structures can be improved.
  • the present invention also provides the preparation method of the high-solid low-VOC steel structure protective coating described in the above technical solution, comprising the following steps:
  • the slurry, the remaining high-solid and low-viscosity alkyd resin, the drier, the remaining alcohol ether solvent and the anti-skinning agent are mixed to obtain a protective coating.
  • the part of the high-solid and low-viscosity alkyd resin preferably accounts for 65-75% of the total mass of the high-solid and low-viscosity alkyd resin, more preferably 68-72%, and most preferably 70%.
  • the partial alcohol ether solvent preferably accounts for 75-85% of the total mass of the alcohol ether solvent, more preferably 78-82%, and most preferably 80%.
  • the mixing is preferably stirring and mixing, and the speed of the stirring and mixing is preferably 800-1000 rpm, more preferably 850-1000 rpm, and most preferably 900-1000 rpm; the present invention adopts a high stirring speed, which can improve the raw material dispersion uniformity.
  • the mixing sequence is preferably the first stirring and mixing of part of the high-solid low-viscosity alkyd resin and part of the alcohol ether solvent, followed by the addition of a wetting agent, a dispersant, and organic bentonite for the second stirring and mixing, Then add titanium dioxide and heavy calcium carbonate for the third stirring and mixing.
  • the time for the first stirring, the second stirring and the third stirring is not particularly limited, as long as the raw materials can be uniformly mixed.
  • the present invention adopts the above-mentioned mixing sequence, and can improve the dispersion uniformity of each raw material.
  • the fineness of the slurry is preferably ⁇ 40 ⁇ m.
  • the grinding is preferably performed in a sand mill, and the rotational speed of the grinding machine is preferably 500-600 rpm.
  • the present invention does not limit the grinding time, which can ensure that the fineness of the slurry meets the requirements That's it.
  • the remaining high-solid and low-viscosity alkyd resin preferably accounts for 25-35% of the total mass of the high-solid and low-viscosity alkyd resin, more preferably 28-32%, and most preferably 30%;
  • the total mass of the solids low viscosity alkyd resin and the remaining high solids low viscosity alkyd resin is calculated as 100%.
  • the part of the alcohol ether solvent preferably accounts for 15-25% of the total mass of the alcohol ether solvent, more preferably 18-22%, and most preferably 20%; the part of the alcohol ether solvent and the alcohol ether
  • the total mass of the solvent-like is calculated as 100%.
  • the mixing is preferably stirring and mixing, and the speed of stirring and mixing is not particularly limited in the present invention, and a stirring speed well known in the art can be used.
  • the mixing sequence is preferably as follows: stirring and mixing the slurry, the remaining high-solid low-viscosity alkyd resin and the drier, adding the remaining alcohol ether solvent to adjust the viscosity, and then adding the anti-skinning agent and stirring and mixing for 15 minutes .
  • the present invention preferably further includes packaging the obtained steel structure protective coating.
  • the present invention does not specifically limit the packaging, and a packaging method well known in the art may be used.
  • the viscosity of the steel structure protective coating provided by the present invention at 25°C is preferably 190-210s.
  • the high-solid and low-viscosity alkyd resin is added in two steps, and the first addition of the high-solid and low-viscosity alkyd resin is to mix with the wetting agent, dispersant, organic bentonite, titanium dioxide and heavy calcium carbonate evenly Dispersion, the second addition of high-solid and low-viscosity alkyd resin is to increase the gloss, hardness, weather resistance and other properties of the coating; if it is added at one time, it will increase the dispersion time and cause uneven dispersion, which will affect the raw materials in the coating.
  • the preparation method provided by the invention is simple in process, and the prepared high-solid low-VOC protective coating is harmless to the environment and human body, and is green, safe and environmentally friendly.
  • the present invention also provides the application of the high-solid low-VOC protective coating described in the above technical solution or the high-solid low-VOC protective coating prepared by the preparation method described in the above technical solution in industrial anti-corrosion, preferably in the application of steel structure anti-corrosion.
  • linseed oil is reacted under 200 DEG C of conditions for 10h, and diethylene glycol butyl ether is used to adjust the resin viscosity to 220s to obtain high-solid low-viscosity alkyd resin;
  • Alcohol ether solvent It is a mixed solvent of diethylene glycol butyl ether: dipropylene glycol butyl ether, and the volume ratio of diethylene glycol butyl ether and dipropylene glycol butyl ether is 3:7;
  • Alcohol ether solvent It is a mixed solvent of diethylene glycol methyl ether, diethylene glycol ethyl ether and tripropylene glycol methyl ether, and the volume ratio of diethylene glycol methyl ether, diethylene glycol ethyl ether and tripropylene glycol methyl ether is 3:3:4;
  • the slurry is pumped into the paint mixing tank through a diaphragm pump or a gear pump, and 18.3 parts of high-solid and low-viscosity alkyd resin and 1 part of cobalt oxide/manganese oxide/iron oxide/zinc oxide are added.
  • the dry agent is stirred and mixed evenly, 1.4 parts of alcohol ether solvent is added to adjust the viscosity until the viscosity is qualified, 0.3 part of methyl ethyl ketoxime is added, and the mixture is stirred for 15 minutes and then packaged to obtain a protective coating.
  • the alkyd resin protective coating is prepared according to the method of Example 1.
  • the difference from Example 1 is that the alkyd resin is prepared by esterification of polyhydric alcohol with polybasic acid and fatty acid by using fatty acid as raw material by traditional fatty acid method.
  • the flash point of the high-solid low-VOC protective coating provided by the present invention is significantly higher than the required index, and the other technical indicators also meet the requirements. It shows that the high-solid low-VOC protective coating provided by the present invention has a high flash point, is safer in the process of production, transportation and use; has excellent acid resistance, alkali resistance, weather resistance and other properties; and is less toxic and environmentally friendly.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

Provided are a high-solid-content low-VOC protective coating, a preparation method therefor, and the use thereof. The present invention belongs to the technical field of coatings. The high-solid-content low-VOC protective coating provided by the present invention contains, in parts by weight, the following components: 55-65 parts of a high-solid-content low-viscosity alkyd resin, 8-15 parts of heavy calcium carbonate, 6-10 parts of an alcohol ether solvent, 0.3-0.5 parts of organic bentonite, 0.2-0.4 parts of a wetting agent, 0.3-0.5 parts of a dispersing agent, 0.7-1 parts of a drier, and 0.2-0.3 parts of an anti-skinning agent. In the present invention, the high-solid low-VOC protective coating is obtained by using the high-solid low-viscosity alkyd resin as a main body and adding the alcohol ether solvent, the heavy calcium carbonate and the organic bentonite, and under the action of the wetting agent, the dispersing agent, the drier and the anti-skinning agent. The present invention is more environmentally friendly during production, transportation and use, and has excellent properties such as acid resistance, alkali resistance and weather resistance.

Description

一种高固体份低VOC防护涂料及其制备方法和应用A kind of high solid content low VOC protective coating and its preparation method and application
本申请要求于2020年11月17日提交中国专利局、申请号为202011286473.4、发明名称为“一种高固体分低VOC防护涂料及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed on November 17, 2020 with the application number 202011286473.4 and the invention titled "A high-solids and low-VOC protective coating and its preparation method and application", all of which are The contents are incorporated herein by reference.
技术领域technical field
本发明涉及涂料技术领域，尤其涉及一种高固体份低VOC防护涂料及其制备方法和应用。The invention relates to the technical field of coatings, in particular to a high-solid low-VOC protective coating and a preparation method and application thereof.
背景技术Background technique
溶剂型涂料具有高装饰性、耐久的保护性、多功能性，在现代工业、国防、信息、生化、新材料、航空航天、海洋开发、可再生能源开发、环保等领域应用广泛。溶剂型涂料中的有机溶剂发挥着关键性作用，例如，有机溶剂能够降低涂料的表面张力，改善颜料润湿与分散性能，调整成膜物和涂料的黏度，改善涂料的流动性等，使涂料产品满足不同的制漆要求和施工要求。Solvent-based coatings have high decorative, durable protection and versatility, and are widely used in modern industry, national defense, information, biochemistry, new materials, aerospace, marine development, renewable energy development, environmental protection and other fields. Organic solvents in solvent-based coatings play a key role. For example, organic solvents can reduce the surface tension of coatings, improve the wetting and dispersing properties of pigments, adjust the viscosity of film formers and coatings, and improve the fluidity of coatings. Products meet different paint requirements and construction requirements.
然而，现有的溶剂型涂料采用的有机溶剂大部分易燃易挥发、污染环境、对人体有害，尤其是有机溶剂挥发在大气中，对大气造成一次污染，而且有机溶剂在光和氧的作用下产生光化学反应，加速臭氧和剧毒氮氧化物的生成，对大气造成严重的二次污染。现有的高固体份低VOC涂料较传统涂料相比，能相对减少VOC的排放，体积固含量相对偏高，单遍成膜厚，但是仍然达不到工业钢结构防护的要求。However, most of the organic solvents used in the existing solvent-based coatings are flammable and volatile, pollute the environment, and are harmful to human body. Photochemical reactions are generated under the oxidative stress, which accelerates the formation of ozone and highly toxic nitrogen oxides, causing serious secondary pollution to the atmosphere. Compared with traditional coatings, the existing high-solids and low-VOC coatings can relatively reduce VOC emissions, the volume solids content is relatively high, and the single-pass film thickness is still not up to the requirements of industrial steel structure protection.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种高固体份低VOC防护涂料及其制备方法和应用，本发明提供的高固体份低VOC防护涂料防锈效果好、施工方便且更加环保。The purpose of the present invention is to provide a high-solid low-VOC protective coating and a preparation method and application thereof. The high-solid low-VOC protective coating provided by the present invention has good anti-rust effect, is convenient to construct and is more environmentally friendly.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
本发明提供了一种高固体份低VOC防护涂料，包括以下重量份数的组分：The present invention provides a kind of high solid content low VOC protective coating, including the following components by weight:
高固低黏醇酸树脂55～65份；55-65 parts of high-solid and low-viscosity alkyd resin;
重质碳酸钙8～15份；8-15 parts of heavy calcium carbonate;
醇醚类溶剂6～10份；6-10 parts of alcohol ether solvent;
润湿剂0.2～0.4份；Wetting agent 0.2 to 0.4 parts;
有机膨润土0.3～0.5份；0.3 to 0.5 parts of organic bentonite;
分散剂0.3～0.5；Dispersant 0.3～0.5;
催干剂0.7～1份；0.7～1 part of drier;
防结皮剂0.2～0.3份。Anti-skinning agent 0.2 to 0.3 parts.
优选的，所述高固低黏醇酸树脂为天然植物油经高温反应制备得到；Preferably, the high-solid and low-viscosity alkyd resin is prepared from natural vegetable oil through high temperature reaction;
所述高温反应的温度为180～250℃，时间为7～11h。The temperature of the high-temperature reaction is 180-250° C., and the time is 7-11 h.
优选的，所述高温反应后还包括加入二乙二醇丁醚和/或二乙二醇甲醚溶剂调整所得树脂的粘度。Preferably, after the high-temperature reaction, the addition of diethylene glycol butyl ether and/or diethylene glycol methyl ether solvent is also included to adjust the viscosity of the obtained resin.
优选的所述天然植物油包括大豆油、亚麻油和棉籽油中的一种或几种。The preferred natural vegetable oils include one or more of soybean oil, linseed oil and cottonseed oil.
优选的，所述高固低黏醇酸树脂在105℃烘烤1h下的固含量为70±2％，在25℃下的粘度为200～250s。Preferably, the solid content of the high-solid and low-viscosity alkyd resin is 70±2% when baked at 105°C for 1 hour, and the viscosity at 25°C is 200-250s.
优选的，还包含15～20份的钛白粉，所述钛白粉为金红石型钛白粉，粒径为10～100nm。Preferably, 15-20 parts of titanium dioxide are also included, and the titanium dioxide is rutile type titanium dioxide with a particle size of 10-100 nm.
优选的，所述重质碳酸钙的粒径为1100～1300目。Preferably, the particle size of the ground calcium carbonate is 1100-1300 mesh.
优选的，所述醇醚类溶剂包括二乙二醇甲醚、二乙二醇乙醚、二乙二醇丁醚、二丙二醇甲醚、二丙二醇丁醚、二甘醇乙醚和三丙二醇甲醚中的一种或几种。Preferably, the alcohol ether solvent includes diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, diethylene glycol ethyl ether and tripropylene glycol methyl ether one or more of them.
优选的，所述润湿剂为硅油；所述分散剂包括磷酸酯类分散剂；所述催干剂包括金属氧化物、金属盐和稀土催干剂中的一种或几种；所述防结皮剂为甲乙酮肟。Preferably, the wetting agent is silicone oil; the dispersant includes a phosphate ester dispersant; the drier includes one or more of metal oxides, metal salts and rare earth driers; The crusting agent is methyl ethyl ketoxime.
优选的，所述金属氧化物和金属盐中的金属独立地包括钴、锰、铁、锌或钙；所述稀土催干剂中的稀土元素包括铈、镧、钇中的一种或几种。Preferably, the metals in the metal oxides and metal salts independently include cobalt, manganese, iron, zinc or calcium; the rare earth elements in the rare earth drier include one or more of cerium, lanthanum and yttrium .
优选的，所述涂料在25℃条件下的粘度为190～210s。Preferably, the viscosity of the coating at 25°C is 190-210s.
本发明提供了上述高固体份低VOC防护涂料的制备方法，包括以下步骤：The present invention provides the preparation method of the above-mentioned high solid content low VOC protective coating, comprises the following steps:
将部分醇醚类溶剂、部分高固低黏醇酸树脂以及剩余组分进行混合后 研磨，得到浆料；所述剩余组分为除了催干剂、防结皮剂、醇醚类溶剂、高固低黏醇酸树脂之外的所有组分；Part of the alcohol ether solvent, part of the high-solid low-viscosity alkyd resin and the remaining components are mixed and then ground to obtain a slurry; All components other than solid low viscosity alkyd resin;
将所述浆料、剩余高固低黏醇酸树脂、催干剂、剩余醇醚类溶剂和防结皮剂混合，得到防护涂料。The slurry, the remaining high-solid and low-viscosity alkyd resin, the drier, the remaining alcohol ether solvent and the anti-skinning agent are mixed to obtain a protective coating.
优选的，所述部分醇醚类溶剂占醇醚类溶剂总质量的75～85％；Preferably, the part of the alcohol ether solvent accounts for 75-85% of the total mass of the alcohol ether solvent;
所述部分高固低黏醇酸树脂占高固低黏醇酸树脂总质量的65～75％；所述浆料细度≤40μm。The part of the high-solid and low-viscosity alkyd resin accounts for 65-75% of the total mass of the high-solid and low-viscosity alkyd resin; the fineness of the slurry is less than or equal to 40 μm.
优选的，所述将部分醇醚类溶剂、部分高固低黏醇酸树脂以及剩余组分进行混合时，所述混合的速度为80～1000rpm。Preferably, when part of the alcohol ether solvent, part of the high-solid and low-viscosity alkyd resin and the remaining components are mixed, the mixing speed is 80-1000 rpm.
本发明提供了上述高固体份低VOC防护涂料在工业防腐中的应用。The present invention provides the application of the above-mentioned high-solid low-VOC protective coating in industrial anti-corrosion.
优选的，所述工业防腐为钢结构防护。Preferably, the industrial anticorrosion is steel structure protection.
本发明提供了一种高固低黏醇酸树脂的制备方法，包括以下步骤：The invention provides a preparation method of high-solid low-viscosity alkyd resin, comprising the following steps:
天然植物油经高温反应，制备得到高固低黏醇酸树脂；Natural vegetable oil is reacted at high temperature to prepare high solid and low viscosity alkyd resin;
所述高温反应的温度为180～250℃，时间为7～11h。The temperature of the high-temperature reaction is 180-250° C., and the time is 7-11 h.
优选的，所述高温反应后还包括加入二乙二醇丁醚和/或二乙二醇甲醚溶剂调整所得树脂的粘度。Preferably, after the high-temperature reaction, the addition of diethylene glycol butyl ether and/or diethylene glycol methyl ether solvent is also included to adjust the viscosity of the obtained resin.
优选的，所述天然植物油包括大豆油、亚麻油和棉籽油中的一种或几种。Preferably, the natural vegetable oil includes one or more of soybean oil, linseed oil and cottonseed oil.
本发明的有益效果：Beneficial effects of the present invention:
本发明以高固低黏醇酸树脂为主体，并添加醇醚类溶剂、重质碳酸钙、有机膨润土，在润湿剂、分散剂、催干剂和防结皮剂的作用下，得到的防护涂料固体份高，属于环保型防护涂料；附着力、柔韧性、耐碱性、耐酸性、耐磨性和耐候性好，而且毒性小，绿色环保，同时其硬度高、漆膜平滑细致、无毒、无污染，且可以有效延长高固体份低VOC防护涂料的漆膜寿命。The present invention takes high-solid and low-viscosity alkyd resin as the main body, and adds alcohol ether solvent, heavy calcium carbonate, organic bentonite, under the action of wetting agent, dispersant, drier and anti-skinning agent, the obtained The protective coating has high solid content and is an environmentally friendly protective coating; good adhesion, flexibility, alkali resistance, acid resistance, abrasion resistance and weather resistance, and low toxicity, green environmental protection, and high hardness, smooth and delicate paint film, It is non-toxic, non-polluting, and can effectively extend the life of the high solids and low VOC protective coatings.
本发明提供了所述高固体份低VOC防护涂料的制备方法，操作简单，适宜规模化生产。The invention provides the preparation method of the high-solid low-VOC protective coating, which is simple to operate and suitable for large-scale production.
具体实施方式Detailed ways
本发明提供了一种高固体份低VOC防护涂料，包括以下重量份数的组分：The present invention provides a kind of high solid content low VOC protective coating, including the following components by weight:
高固低黏醇酸树脂55～65份；55-65 parts of high-solid and low-viscosity alkyd resin;
重质碳酸钙8～15份；8-15 parts of heavy calcium carbonate;
醇醚类溶剂6～10份；6-10 parts of alcohol ether solvent;
润湿剂0.2～0.4份；Wetting agent 0.2 to 0.4 parts;
分散剂0.3～0.5；Dispersant 0.3～0.5;
有机膨润土0.3～0.5份；0.3 to 0.5 parts of organic bentonite;
催干剂0.7～1份；0.7～1 part of drier;
防结皮剂0.2～0.3份。Anti-skinning agent 0.2 to 0.3 parts.
在本发明中，若无特殊说明，所有的原料组分均为本领域技术人员熟知的市售商品。In the present invention, unless otherwise specified, all raw material components are commercially available commodities well known to those skilled in the art.
在本发明中，按重量份数计，制备所述高固体份低VOC防护涂料的原料包括高固低黏醇酸树脂55～65份，优选为60～65份。在本发明中，所述高固低黏醇酸树脂的用量过多，醇酸树脂防护涂料不易干燥；用量过少，钢结构防护涂料漆膜丰满度较差。在本发明中，所述高固低黏醇酸树脂优选为天然植物油经高温反应制备得到。在本发明中，所述高温反应过程中，天然植物油先发生醇解，然后进行聚合。在本发明中，所述天然植物油优选包括大豆油、亚麻油和棉籽油中的一种或几种，更优选为大豆油、亚麻油或棉籽油。在本发明中，所述高温反应的温度优选为180～250℃，进一步优选为190～220℃；所述高温反应的时间优选为7～11h，进一步优选为8～10h。完成所述高温反应后，本发明优选还包括加入二乙二醇丁醚和/或二乙二醇甲醚溶剂调整所得树脂的粘度；本发明中，所述高固低黏醇酸树脂的固含量优选为70±2％(105℃烘烤1h)，粘度优选为200～250s(涂-4粘度计，25℃)。In the present invention, in parts by weight, the raw materials for preparing the high-solids and low-VOC protective coatings include 55-65 parts, preferably 60-65 parts, of high-solids and low-viscosity alkyd resins. In the present invention, if the dosage of the high-solid and low-viscosity alkyd resin is too much, the alkyd resin protective coating is not easy to dry; if the dosage is too small, the fullness of the paint film of the steel structure protective coating is poor. In the present invention, the high-solid and low-viscosity alkyd resin is preferably prepared from natural vegetable oil through high temperature reaction. In the present invention, during the high temperature reaction, the natural vegetable oil undergoes alcoholysis first, and then undergoes polymerization. In the present invention, the natural vegetable oil preferably includes one or more of soybean oil, linseed oil and cottonseed oil, more preferably soybean oil, linseed oil or cottonseed oil. In the present invention, the temperature of the high-temperature reaction is preferably 180-250°C, more preferably 190-220°C; the time of the high-temperature reaction is preferably 7-11 h, more preferably 8-10 h. After completing the high temperature reaction, the present invention preferably further includes adding diethylene glycol butyl ether and/or diethylene glycol methyl ether solvent to adjust the viscosity of the obtained resin; The content is preferably 70±2% (baking at 105°C for 1 h), and the viscosity is preferably 200-250s (coating-4 viscometer, 25°C).
在本发明中，以所述高固低黏醇酸树脂的重量份数为基准，制备所述防护涂料的原料包括重质碳酸钙8～15份，优选为8～13份。在本发明中，所述重质碳酸钙的粒径优选为1100～1300目，更优选为1200目。在本发明中，所述重质碳酸钙作为体质颜料，用量过多会影响钢结构防护涂料成膜效果，用量过少会影响钢结构防护涂料漆膜的机械性能。本发明将重质碳酸钙与其他原料配合使用，能够提高钢结构防护涂料的性能。In the present invention, based on the parts by weight of the high-solid and low-viscosity alkyd resin, the raw materials for preparing the protective coating include 8-15 parts of heavy calcium carbonate, preferably 8-13 parts. In the present invention, the particle size of the ground calcium carbonate is preferably 1100-1300 mesh, more preferably 1200 mesh. In the present invention, the heavy calcium carbonate is used as an extender pigment. Too much dosage will affect the film-forming effect of the steel structure protective paint, and too little dosage will affect the mechanical properties of the steel structure protective paint film. In the present invention, the heavy calcium carbonate is used in combination with other raw materials, and the performance of the steel structure protective coating can be improved.
在本发明中，以所述高固低黏醇酸树脂的重量份数为基准，制备所述 防护涂料的原料包括醇醚类溶剂6～10份，优选为7～9份。在本发明中，所述醇醚类溶剂优选包括二乙二醇甲醚、二乙二醇乙醚、二乙二醇丁醚、二丙二醇甲醚、二丙二醇丁醚、二甘醇乙醚和三丙二醇甲醚中的一种或几种。在本发明中，所述醇醚类溶剂的用量过多或过少均会影响钢结构防护涂料的粘度，进而影响其成膜效果和性能。本发明将醇醚类溶剂与其他原料配合使用，能够提高钢结构防护涂料的性能。In the present invention, based on the parts by weight of the high-solid low-viscosity alkyd resin, the raw materials for preparing the protective coating include 6-10 parts, preferably 7-9 parts, of alcohol ether solvents. In the present invention, the alcohol ether solvent preferably includes diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, diethylene glycol ethyl ether and tripropylene glycol One or more of methyl ethers. In the present invention, too much or too little amount of the alcohol ether solvent will affect the viscosity of the steel structure protective coating, and then affect its film-forming effect and performance. In the invention, the alcohol ether solvent is used in combination with other raw materials, so that the performance of the steel structure protective coating can be improved.
在本发明中，以所述高固低黏醇酸树脂的重量份数为基准，制备所述防护涂料的原料包括有机膨润土0.3～0.5份，优选为0.32～0.4份，更优选为0.32份、0.34份、0.36份、0.38份或0.40份。在本发明中，所述有机膨润土的作用是防止其他原料沉淀；所述有机膨润土的用量过多会导致钢结构防护涂料的粘度过大，用量过少起不到防沉效果。本发明将有机膨润土与其他原料配合使用，能够提高钢结构防护涂料的性能。In the present invention, based on the parts by weight of the high-solid and low-viscosity alkyd resin, the raw materials for preparing the protective coating include 0.3-0.5 parts of organic bentonite, preferably 0.32-0.4 parts, more preferably 0.32 parts, 0.34 servings, 0.36 servings, 0.38 servings or 0.40 servings. In the present invention, the function of the organobentonite is to prevent the precipitation of other raw materials; if the amount of the organobentonite is too large, the viscosity of the steel structure protective coating will be too large, and the amount of the organic bentonite will be too small, and the anti-settling effect will not be achieved. In the present invention, the organic bentonite is used in combination with other raw materials, and the performance of the steel structure protective coating can be improved.
在本发明中，以所述高固低黏醇酸树脂的重量份数为基准，制备所述防护涂料的原料包括润湿剂0.2～0.4份，优选为0.22～0.4份，更优选为0.25份、0.3份、0.35份或0.40份。本发明所述润湿剂优选为硅油。在本发明中，所述硅油能够很好的润湿颜填料，进而有利于提高钛白粉、重质碳酸钙的研磨效率以及低粘度醇酸树脂对其他原料的包覆，防止钛白粉、重质碳酸钙等原料浮色；所述润湿剂的用量过多会导致钢结构防护涂料漆膜缩孔，用量过少会导致钢结构防护涂料漆膜发花。本发明将润湿剂与其他原料配合使用，能够提高钢结构防护涂料的性能。In the present invention, based on the parts by weight of the high-solid and low-viscosity alkyd resin, the raw materials for preparing the protective coating include 0.2-0.4 parts of wetting agent, preferably 0.22-0.4 parts, more preferably 0.25 parts , 0.3 servings, 0.35 servings or 0.40 servings. The wetting agent of the present invention is preferably silicone oil. In the present invention, the silicone oil can well wet the pigments and fillers, thereby helping to improve the grinding efficiency of titanium dioxide and heavy calcium carbonate and the coating of other raw materials by low-viscosity alkyd resin, preventing titanium dioxide, heavy Calcium carbonate and other raw materials float color; too much amount of the wetting agent will cause shrinkage of the steel structure protective paint film, and too little amount will cause the steel structure protective paint film to bloom. In the invention, the wetting agent is used in combination with other raw materials, and the performance of the protective coating for steel structures can be improved.
在本发明中，以所述高固低黏醇酸树脂的重量份数为基准，制备所述防护涂料的原料包括分散剂0.3～0.5份，优选为0.35～0.5份，更优选为0.35份、0.4份、0.45份或0.5份。在本发明中，所述分散剂优选包括磷酸酯类分散剂，优选为DisperBYK-110或DisperBYK-111型分散剂。在本发明中，所述分散剂的作用是分散颜填料；所述分散剂的用量过多会导致钢结构防护涂料漆膜干性较慢，用量过少会导致钢结构防护涂料漆膜浮色、涂料沉淀。本发明将分散剂与其他原料配合使用，能够提高钢结构防护涂料的性能。In the present invention, based on the parts by weight of the high-solid low-viscosity alkyd resin, the raw materials for preparing the protective coating include 0.3-0.5 parts of dispersant, preferably 0.35-0.5 parts, more preferably 0.35 parts, 0.4 servings, 0.45 servings or 0.5 servings. In the present invention, the dispersant preferably includes a phosphoric acid ester type dispersant, preferably a DisperBYK-110 or DisperBYK-111 type dispersant. In the present invention, the function of the dispersant is to disperse pigments and fillers; if the amount of the dispersant is too much, the drying of the steel structure protective paint film will be slow, and if the amount is too small, the color of the steel structure protective paint film will float. , paint precipitation. In the present invention, the dispersant is used in combination with other raw materials, and the performance of the protective coating for steel structures can be improved.
在本发明中，以所述高固低黏醇酸树脂的重量份数为基准，制备所述防护涂料的原料包括催干剂0.7～1份，优选为0.75～1份，更优选为0.75 份、0.8份、0.85份、0.9份、0.95份或1份。在本发明中，所述催干剂包括金属氧化物、金属盐和稀土催干剂中的一种或几种；所述金属氧化物和金属盐中的金属独立地包括钴、锰、铁、锌或钙。所述稀土催干剂中的稀土元素包括铈、镧、钇中的一种或几种。在本发明中，所述催干剂的作用是加快钢结构防护涂料漆膜干燥；所述催干剂的用量过多会导致钢结构防护涂料易结皮，用量过少会导致钢结构防护涂料漆膜不易干燥。本发明将催干剂与其他原料配合使用，能够提高钢结构防护涂料的性能。In the present invention, based on the parts by weight of the high-solid low-viscosity alkyd resin, the raw materials for preparing the protective coating include 0.7-1 part, preferably 0.75-1 part, and more preferably 0.75 part of a drier. , 0.8 servings, 0.85 servings, 0.9 servings, 0.95 servings or 1 serving. In the present invention, the drier includes one or more of metal oxides, metal salts and rare earth driers; the metals in the metal oxides and metal salts independently include cobalt, manganese, iron, Zinc or calcium. The rare earth element in the rare earth drier includes one or more of cerium, lanthanum and yttrium. In the present invention, the role of the drier is to speed up the drying of the steel structure protective paint film; the excessive amount of the drier will cause the steel structure protective paint to be easily crusted, and the excessive amount will lead to the steel structure protective paint. The paint film is not easy to dry. In the present invention, the drier is used in combination with other raw materials, and the performance of the steel structure protective coating can be improved.
在本发明中，以所述高固低黏醇酸树脂的重量份数为基准，制备所述防护涂料的原料包括防结皮剂0.2～0.3份，优选为0.22～0.3份，更优选为0.22份、0.24份、0.26份、0.28份或0.3份。本发明所述防结皮剂优选为甲乙酮肟。在本发明中，所述甲乙酮肟的作用是防止钢结构防护涂料在储存过程中结皮；所述防结皮剂的用量过多会导致钢结构防护涂料漆膜不干，用量过少不能达到防结皮的效果。本发明将防结皮剂与其他原料配合使用，能够提高钢结构防护涂料的性能。In the present invention, based on the parts by weight of the high-solid low-viscosity alkyd resin, the raw materials for preparing the protective coating include 0.2-0.3 parts of anti-skinning agent, preferably 0.22-0.3 parts, more preferably 0.22 parts serving, 0.24 serving, 0.26 serving, 0.28 serving, or 0.3 serving. The anti-skinning agent of the present invention is preferably methyl ethyl ketoxime. In the present invention, the role of the methyl ethyl ketoxime is to prevent the steel structure protective coating from crusting during storage; the excessive dosage of the anti-skinning agent will cause the steel structure protective coating paint film to not dry, and the dosage is too small to achieve Anti-skinning effect. In the invention, the anti-skinning agent is used in combination with other raw materials, and the performance of the steel structure protective coating can be improved.
在本发明中，以所述高固低黏醇酸树脂的重量份数为基准，制备所述防护涂料的原料包括钛白粉15～20份，优选为15～18份。在本发明中，所述钛白粉作为着色颜料，用量过多会影响钢结构防护涂料生产成本，用量过少会影响钢结构防护涂料遮盖力。在本发明中，所述钛白粉优选为金红石型钛白粉，更优选为氯化法金红石型钛白粉。本发明将钛白粉与其他原料配合使用，能够提高钢结构防护涂料的性能。In the present invention, based on the parts by weight of the high-solid and low-viscosity alkyd resin, the raw materials for preparing the protective coating include 15-20 parts of titanium dioxide, preferably 15-18 parts. In the present invention, the titanium dioxide is used as a coloring pigment. Too much dosage will affect the production cost of the steel structure protective coating, and too little dosage will affect the hiding power of the steel structure protective coating. In the present invention, the titanium dioxide is preferably a rutile type titanium dioxide, more preferably a chloride method rutile type titanium dioxide. In the invention, the titanium dioxide is used in combination with other raw materials, and the performance of the protective coating for steel structures can be improved.
本发明还提供了上述技术方案所述高固体份低VOC钢结构防护涂料的制备方法，包括以下步骤：The present invention also provides the preparation method of the high-solid low-VOC steel structure protective coating described in the above technical solution, comprising the following steps:
将部分醇醚类溶剂、部分高固低黏醇酸树脂以及剩余组分进行混合后研磨，得到浆料；所述剩余组分为除了催干剂、防结皮剂、醇醚类溶剂、高固低黏醇酸树脂之外的所有组分；Part of the alcohol ether solvent, part of the high-solid low-viscosity alkyd resin and the remaining components are mixed and then ground to obtain a slurry; All components other than solid low viscosity alkyd resin;
将所述浆料、剩余高固低黏醇酸树脂、催干剂、剩余醇醚类溶剂和防结皮剂混合，得到防护涂料。The slurry, the remaining high-solid and low-viscosity alkyd resin, the drier, the remaining alcohol ether solvent and the anti-skinning agent are mixed to obtain a protective coating.
在本发明中，所述部分高固低黏醇酸树脂优选占高固低黏醇酸树脂总质量的65～75％，更优选为68～72％，最优选为70％。在本发明中，所述部分醇醚类溶剂优选占醇醚类溶剂总质量的75～85％，更优选为78～82％， 最优选为80％。In the present invention, the part of the high-solid and low-viscosity alkyd resin preferably accounts for 65-75% of the total mass of the high-solid and low-viscosity alkyd resin, more preferably 68-72%, and most preferably 70%. In the present invention, the partial alcohol ether solvent preferably accounts for 75-85% of the total mass of the alcohol ether solvent, more preferably 78-82%, and most preferably 80%.
在本发明中，所述混合优选为搅拌混合，所述搅拌混合的速度优选为800～1000rpm，更优选为850～1000rpm，最优选为900～1000rpm；本发明采用高的搅拌速度，能够提高原料的分散均匀性。在本发明中，所述混合的顺序优选为将部分高固低黏醇酸树脂和部分醇醚类溶剂进行第一搅拌混合，依次加入润湿剂、分散剂、有机膨润土进行第二搅拌混合，然后再加入钛白粉和重质碳酸钙进行第三搅拌混合。本发明中对于第一搅拌混合、第二搅拌混合和第三搅拌混合的时间没有特殊限定，能够保证原料混合均匀即可。本发明采用上述混合顺序，能够提高各原料的分散均匀性。In the present invention, the mixing is preferably stirring and mixing, and the speed of the stirring and mixing is preferably 800-1000 rpm, more preferably 850-1000 rpm, and most preferably 900-1000 rpm; the present invention adopts a high stirring speed, which can improve the raw material dispersion uniformity. In the present invention, the mixing sequence is preferably the first stirring and mixing of part of the high-solid low-viscosity alkyd resin and part of the alcohol ether solvent, followed by the addition of a wetting agent, a dispersant, and organic bentonite for the second stirring and mixing, Then add titanium dioxide and heavy calcium carbonate for the third stirring and mixing. In the present invention, the time for the first stirring, the second stirring and the third stirring is not particularly limited, as long as the raw materials can be uniformly mixed. The present invention adopts the above-mentioned mixing sequence, and can improve the dispersion uniformity of each raw material.
在本发明中，所述浆料细度优选≤40μm。在本发明中，所述研磨优选在砂磨机中进行，所述研磨机的转速优选为500～600rpm，本发明对于所述研磨的时间没有特殊限定，能够保证所述浆料细度达到要求即可。In the present invention, the fineness of the slurry is preferably ≤40 μm. In the present invention, the grinding is preferably performed in a sand mill, and the rotational speed of the grinding machine is preferably 500-600 rpm. The present invention does not limit the grinding time, which can ensure that the fineness of the slurry meets the requirements That's it.
在本发明中，所述剩余高固低粘醇酸树脂优选占高固低黏醇酸树脂总质量的25～35％，更优选为28～32％，最优选为30％；所述部分高固低黏醇酸树脂和剩余高固低黏醇酸树脂的总质量计为100％。在本发明中，所述部分醇醚类溶剂优选占醇醚类溶剂总质量的15～25％，更优选为18～22％，最优选为20％；所述部分醇醚类溶剂和醇醚类溶剂的总质量计为100％。In the present invention, the remaining high-solid and low-viscosity alkyd resin preferably accounts for 25-35% of the total mass of the high-solid and low-viscosity alkyd resin, more preferably 28-32%, and most preferably 30%; The total mass of the solids low viscosity alkyd resin and the remaining high solids low viscosity alkyd resin is calculated as 100%. In the present invention, the part of the alcohol ether solvent preferably accounts for 15-25% of the total mass of the alcohol ether solvent, more preferably 18-22%, and most preferably 20%; the part of the alcohol ether solvent and the alcohol ether The total mass of the solvent-like is calculated as 100%.
在本发明中，所述混合优选为搅拌混合，本发明对于搅拌混合的速度没有特殊限定，采用本领域熟知的搅拌速度即可。In the present invention, the mixing is preferably stirring and mixing, and the speed of stirring and mixing is not particularly limited in the present invention, and a stirring speed well known in the art can be used.
在本发明中，所述混合的顺序优选为将浆料、剩余的高固低黏醇酸树脂和催干剂搅拌混合，加入剩余醇醚类溶剂调节粘度，然后加入防结皮剂搅拌混合15min。In the present invention, the mixing sequence is preferably as follows: stirring and mixing the slurry, the remaining high-solid low-viscosity alkyd resin and the drier, adding the remaining alcohol ether solvent to adjust the viscosity, and then adding the anti-skinning agent and stirring and mixing for 15 minutes .
完成所述混合后，本发明优选还包括将所得钢结构防护涂料进行包装。本发明对于所述包装没有特殊限定，采用本领域熟知的包装方式即可。After the mixing is completed, the present invention preferably further includes packaging the obtained steel structure protective coating. The present invention does not specifically limit the packaging, and a packaging method well known in the art may be used.
本发明提供的钢结构防护涂料在25℃条件下的粘度优选为190～210s。The viscosity of the steel structure protective coating provided by the present invention at 25°C is preferably 190-210s.
本发明提供的制备方法中高固低黏醇酸树脂分两次加入，第一次加入高固低黏醇酸树脂是为了与润湿剂、分散剂、有机膨润土、钛白粉和重质碳酸钙均匀分散，第二次加入高固低黏醇酸树脂是为增加涂料的光泽、硬 度、耐候性等性能；若一次性加入，一是增加分散时间且会使得分散不均匀，影响涂料中各原料的分散效率，且会造成电、冷却水和设备的损耗，大大提高生产成本；二是会导致涂料性能不达标。采用本发明提供的制备方法工艺简单，制备的高固体份低VOC防护涂料对环境和人体无害，绿色、安全、环保。In the preparation method provided by the present invention, the high-solid and low-viscosity alkyd resin is added in two steps, and the first addition of the high-solid and low-viscosity alkyd resin is to mix with the wetting agent, dispersant, organic bentonite, titanium dioxide and heavy calcium carbonate evenly Dispersion, the second addition of high-solid and low-viscosity alkyd resin is to increase the gloss, hardness, weather resistance and other properties of the coating; if it is added at one time, it will increase the dispersion time and cause uneven dispersion, which will affect the raw materials in the coating. Dispersion efficiency, and will cause the loss of electricity, cooling water and equipment, greatly increase the production cost; second, it will lead to the performance of the coating does not meet the standard. The preparation method provided by the invention is simple in process, and the prepared high-solid low-VOC protective coating is harmless to the environment and human body, and is green, safe and environmentally friendly.
本发明还提供了上述技术方案所述高固体份低VOC防护涂料或上述技术方案所述制备方法制备的高固体份低VOC防护涂料在工业防腐中的应用，优选在钢结构防腐中的应用。The present invention also provides the application of the high-solid low-VOC protective coating described in the above technical solution or the high-solid low-VOC protective coating prepared by the preparation method described in the above technical solution in industrial anti-corrosion, preferably in the application of steel structure anti-corrosion.
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some, but not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
实施例1Example 1
(1)将大豆油在190℃条件下反应11h，采用二乙二醇丁醚调整树脂粘度至200s，得到高固低黏醇酸树脂；(1) The soybean oil was reacted at 190°C for 11h, and the resin viscosity was adjusted to 200s with diethylene glycol butyl ether to obtain a high-solid and low-viscosity alkyd resin;
(2)预分散：按重量份数计，在投料分散缸中加6.3份醇醚类溶剂、45.5份高固低黏醇酸树脂搅拌均匀；依次加入0.25份硅油、0.5份DisperBYK-110型分散剂、0.3份有机膨润土，在1000rpm条件下高速分散15min；然后依次加入15份金红石型钛白粉、10份重质碳酸钙，在1000rpm条件下高速搅拌使至呈均匀状态；其中，醇醚类溶剂为二乙二醇甲醚、三丙二醇甲醚、二甘醇乙醚的混合溶剂，二乙二醇甲醚、三丙二醇甲醚、二甘醇乙醚的体积比为4:4:2；(2) Pre-dispersion: in parts by weight, add 6.3 parts of alcohol ether solvent and 45.5 parts of high-solid low-viscosity alkyd resin to the feeding dispersion tank and stir evenly; add 0.25 parts of silicone oil and 0.5 parts of DisperBYK-110 type dispersion in turn agent, 0.3 parts of organic bentonite, dispersed at a high speed for 15min under the condition of 1000rpm; then added 15 parts of rutile titanium dioxide and 10 parts of heavy calcium carbonate in turn, and stirred at a high speed under the condition of 1000rpm to make a uniform state; among them, alcohol ether solvent It is a mixed solvent of diethylene glycol methyl ether, tripropylene glycol methyl ether and diethylene glycol ethyl ether, and the volume ratio of diethylene glycol methyl ether, tripropylene glycol methyl ether and diethylene glycol ethyl ether is 4:4:2;
(3)研磨：将所得物料用隔膜泵或齿轮泵吸入至砂磨机中，在550rpm条件下研磨至浆料细度≤40μm，得到呈稳定状态的浆料；(3) Grinding: the obtained material is sucked into a sand mill by a diaphragm pump or a gear pump, and ground to a slurry fineness of ≤40 μm under the condition of 550 rpm to obtain a stable slurry;
(4)调漆：将所述浆料通过隔膜泵或齿轮泵打入至调漆缸中，加入19.5份高固低黏醇酸树脂和0.8份氧化钴/氧化铁催干剂搅拌混合均匀，加入1.6份醇醚类溶剂进行调粘至粘度合格，加入0.25份甲乙酮肟搅拌15min后包装，得到防护涂料。(4) Paint mixing: The slurry is pumped into the paint mixing tank through a diaphragm pump or a gear pump, and 19.5 parts of high-solid and low-viscosity alkyd resin and 0.8 parts of cobalt oxide/iron oxide drier are added to stir and mix evenly. Add 1.6 parts of alcohol ether solvent to adjust the viscosity until the viscosity is qualified, add 0.25 parts of methyl ethyl ketoxime and stir for 15 minutes, then package, to obtain a protective coating.
实施例2Example 2
(1)将亚麻油在200℃条件下反应10h，采用二乙二醇丁醚调整树脂粘 度至220s，得到高固低黏醇酸树脂；(1) linseed oil is reacted under 200 DEG C of conditions for 10h, and diethylene glycol butyl ether is used to adjust the resin viscosity to 220s to obtain high-solid low-viscosity alkyd resin;
(2)预分散：按重量份数计，在投料分散缸中加5.8份醇醚类溶剂、42份高固低黏醇酸树脂搅拌均匀；依次加入0.2份硅油、0.4份DisperBYK-111型分散剂、0.3份有机膨润土，在1000rpm条件下高速分散15min；然后依次加入16份金红石型钛白粉、15份重质碳酸钙，在1000rpm条件下高速搅拌使至呈均匀状态；其中，醇醚类溶剂为二乙二醇丁醚：二丙二醇丁醚的混合溶剂，二乙二醇丁醚和二丙二醇丁醚的体积比为3:7；(2) Pre-dispersion: in parts by weight, add 5.8 parts of alcohol ether solvent and 42 parts of high-solids and low-viscosity alkyd resin in the feeding dispersing cylinder and stir evenly; add 0.2 parts of silicone oil and 0.4 parts of DisperBYK-111 type dispersion agent, 0.3 parts of organic bentonite, dispersed at a high speed for 15min under the condition of 1000rpm; then added 16 parts of rutile type titanium dioxide and 15 parts of heavy calcium carbonate in turn, and stirred at a high speed under the condition of 1000rpm to make a uniform state; wherein, alcohol ether solvent It is a mixed solvent of diethylene glycol butyl ether: dipropylene glycol butyl ether, and the volume ratio of diethylene glycol butyl ether and dipropylene glycol butyl ether is 3:7;
(3)研磨：将所得物料用隔膜泵或齿轮泵吸入至砂磨机中，在550rpm条件下研磨至浆料细度≤30μm，得到呈稳定状态的浆料；(3) Grinding: the obtained material is sucked into a sand mill by a diaphragm pump or a gear pump, and ground to a slurry fineness ≤ 30 μm under the condition of 550 rpm to obtain a stable slurry;
(4)调漆：将所述浆料通过隔膜泵或齿轮泵打入至调漆缸中，加入18份高固低黏醇酸树脂和0.7份氧化锌/氧化钙/氧化锰催干剂搅拌混合均匀，加入1.4份醇醚类溶剂进行调粘至粘度合格，加入0.22份甲乙酮肟搅拌15min后包装，得到防护涂料。(4) Paint mixing: The slurry is pumped into the paint mixing tank through a diaphragm pump or a gear pump, and 18 parts of high-solid low-viscosity alkyd resin and 0.7 parts of zinc oxide/calcium oxide/manganese oxide drier are added and stirred Mix uniformly, add 1.4 parts of alcohol ether solvent to adjust the viscosity until the viscosity is qualified, add 0.22 parts of methyl ethyl ketoxime, stir for 15 minutes, and then package to obtain protective paint.
实施例3Example 3
(1)将棉籽油在220℃条件下反应8h，采用二乙二醇丁醚调整树脂粘度至250s，得到高固低黏醇酸树脂；(1) The cottonseed oil was reacted at 220°C for 8h, and diethylene glycol butyl ether was used to adjust the resin viscosity to 250s to obtain a high-solid and low-viscosity alkyd resin;
(2)预分散：按重量份数计，在投料分散缸中加7.9份醇醚类溶剂、44份高固低黏醇酸树脂搅拌均匀；依次加入0.3份硅油、0.5份DisperBYK-110型分散剂、0.35份有机膨润土，在1000rpm条件下高速分散15min；然后依次加入17份金红石型钛白粉、8份重质碳酸钙，在1000rpm条件下高速搅拌使至呈均匀状态；其中，醇醚类溶剂为二乙二醇甲醚、二乙二醇乙醚和三丙二醇甲醚的混合溶剂，二乙二醇甲醚、二乙二醇乙醚和三丙二醇甲醚的体积比为3:3:4；(2) Pre-dispersion: in parts by weight, add 7.9 parts of alcohol ether solvent and 44 parts of high-solid and low-viscosity alkyd resin to the feeding dispersion tank and stir evenly; add 0.3 parts of silicone oil and 0.5 parts of DisperBYK-110 type dispersion agent, 0.35 parts of organic bentonite, dispersed at high speed for 15min under the condition of 1000rpm; then added 17 parts of rutile titanium dioxide and 8 parts of heavy calcium carbonate in turn, and stirred at high speed under the condition of 1000rpm to make it uniform; wherein, alcohol ether solvent It is a mixed solvent of diethylene glycol methyl ether, diethylene glycol ethyl ether and tripropylene glycol methyl ether, and the volume ratio of diethylene glycol methyl ether, diethylene glycol ethyl ether and tripropylene glycol methyl ether is 3:3:4;
(3)研磨：将所得物料用隔膜泵或齿轮泵吸入至砂磨机中，在550rpm条件下研磨至浆料细度≤30μm，得到呈稳定状态的浆料；(3) Grinding: the obtained material is sucked into a sand mill by a diaphragm pump or a gear pump, and ground to a slurry fineness ≤ 30 μm under the condition of 550 rpm to obtain a stable slurry;
(4)调漆：将所述浆料通过隔膜泵或齿轮泵打入至调漆缸中，加入19份高固低黏醇酸树脂和0.75份稀土催干剂搅拌混合均匀，加入2份醇醚类溶剂进行调粘至粘度合格，加入0.2份甲乙酮肟搅拌15min后包装，得到防护涂料；其中稀土催干剂中的稀土元素为铈。(4) Paint mixing: the slurry is pumped into the paint mixing tank through a diaphragm pump or a gear pump, 19 parts of high-solid and low-viscosity alkyd resin and 0.75 parts of rare earth drier are added, stirred and mixed evenly, and 2 parts of alcohol are added. The ether solvent is adjusted to the viscosity until the viscosity is qualified, and 0.2 part of methyl ethyl ketoxime is added and stirred for 15 minutes and then packaged to obtain a protective coating; wherein the rare earth element in the rare earth drier is cerium.
实施例4Example 4
(1)将棉籽油和大豆油在210℃条件下反应9h，采用二乙二醇丁醚调整树脂粘度至240s，得到高固低黏醇酸树脂；(1) The cottonseed oil and soybean oil were reacted at 210°C for 9 hours, and diethylene glycol butyl ether was used to adjust the resin viscosity to 240s to obtain a high-solid and low-viscosity alkyd resin;
(2)预分散：按重量份数计，在投料分散缸中加5.5份醇醚类溶剂、42.7份高固低黏醇酸树脂搅拌均匀；依次加入0.3份硅油、0.3份DisperBYK-111型分散剂、0.3份有机膨润土，在1000rpm条件下高速分散15min；然后依次加入18份金红石型钛白粉、12份重质碳酸钙，在1000rpm条件下高速搅拌使至呈均匀状态；其中，醇醚类溶剂为二丙二醇甲醚和二甘醇乙醚的混合溶剂，二丙二醇甲醚和二甘醇乙醚的体积比为1:1；(2) Pre-dispersion: in parts by weight, add 5.5 parts of alcohol ether solvent and 42.7 parts of high-solid low-viscosity alkyd resin to the feeding dispersion tank and stir evenly; add 0.3 parts of silicone oil and 0.3 parts of DisperBYK-111 type dispersion in turn agent, 0.3 parts of organic bentonite, dispersed at a high speed for 15min under the condition of 1000rpm; then added 18 parts of rutile type titanium dioxide and 12 parts of heavy calcium carbonate in turn, and stirred at a high speed under the condition of 1000rpm to a uniform state; wherein, alcohol ether solvent It is a mixed solvent of dipropylene glycol methyl ether and diethylene glycol ethyl ether, and the volume ratio of dipropylene glycol methyl ether and diethylene glycol ethyl ether is 1:1;
(3)研磨：将所得物料用隔膜泵或齿轮泵吸入至砂磨机中，在550rpm条件下研磨至浆料细度≤30μm，得到呈稳定状态的浆料；(3) Grinding: the obtained material is sucked into a sand mill by a diaphragm pump or a gear pump, and ground to a slurry fineness ≤ 30 μm under the condition of 550 rpm to obtain a stable slurry;
(4)调漆：将所述浆料通过隔膜泵或齿轮泵打入至调漆缸中，加入18.3份高固低黏醇酸树脂和1份氧化钴/氧化锰/氧化铁/氧化锌催干剂搅拌混合均匀，加入1.4份醇醚类溶剂进行调粘至粘度合格，加入0.3份甲乙酮肟搅拌15min后包装，得到防护涂料。(4) Paint mixing: the slurry is pumped into the paint mixing tank through a diaphragm pump or a gear pump, and 18.3 parts of high-solid and low-viscosity alkyd resin and 1 part of cobalt oxide/manganese oxide/iron oxide/zinc oxide are added. The dry agent is stirred and mixed evenly, 1.4 parts of alcohol ether solvent is added to adjust the viscosity until the viscosity is qualified, 0.3 part of methyl ethyl ketoxime is added, and the mixture is stirred for 15 minutes and then packaged to obtain a protective coating.
对照例1Comparative Example 1
按照实施例1的方法制备醇酸树脂防护涂料，与实施例1的区别在于，采用传统的脂肪酸法以脂肪酸为原料，将多元醇与多元酸、脂肪酸进行酯化反应来制备醇酸树脂。The alkyd resin protective coating is prepared according to the method of Example 1. The difference from Example 1 is that the alkyd resin is prepared by esterification of polyhydric alcohol with polybasic acid and fatty acid by using fatty acid as raw material by traditional fatty acid method.
测试例1Test Example 1
将实施例1～4和对照例1制备的防护涂料进行性能测试，测试结果如表1所示。The protective coatings prepared in Examples 1 to 4 and Comparative Example 1 were tested for performance, and the test results are shown in Table 1.
表1实施例1～4和对照例1制备的防护涂料的性能测试结果Table 1 Performance test results of protective coatings prepared in Examples 1 to 4 and Comparative Example 1
Figure PCTCN2021099700-appb-000001
Figure PCTCN2021099700-appb-000001
Figure PCTCN2021099700-appb-000002
Figure PCTCN2021099700-appb-000002
Figure PCTCN2021099700-appb-000003
Figure PCTCN2021099700-appb-000003
由表1可知，本发明提供的高固体份低VOC防护涂料的闪点大幅度的高于要求的指标，其余各项技术指标也均符合要求。表明，本发明提供的高固体份低VOC防护涂料闪点高，在生产、运输和使用的过程中更加安全；耐酸、耐碱、耐候性等性能优异；而且毒性小，绿色环保。As can be seen from Table 1, the flash point of the high-solid low-VOC protective coating provided by the present invention is significantly higher than the required index, and the other technical indicators also meet the requirements. It shows that the high-solid low-VOC protective coating provided by the present invention has a high flash point, is safer in the process of production, transportation and use; has excellent acid resistance, alkali resistance, weather resistance and other properties; and is less toxic and environmentally friendly.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.

Claims (19)

  1. 一种高固体份低VOC防护涂料，其特征在于，包括以下重量份数的组分：A kind of high solid content low VOC protective coating is characterized in that, comprises the following components by weight:
    高固低黏醇酸树脂55～65份；55-65 parts of high-solid and low-viscosity alkyd resin;
    重质碳酸钙8～15份；8-15 parts of heavy calcium carbonate;
    醇醚类溶剂6～10份；6-10 parts of alcohol ether solvent;
    润湿剂0.2～0.4份；Wetting agent 0.2 to 0.4 parts;
    有机膨润土0.3～0.5份；0.3 to 0.5 parts of organic bentonite;
    分散剂0.3～0.5；Dispersant 0.3～0.5;
    催干剂0.7～1份；0.7～1 part of drier;
    防结皮剂0.2～0.3份。Anti-skinning agent 0.2 to 0.3 parts.
  2. 根据权利要求1所述的高固体份低VOC防护涂料，其特征在于，所述高固低黏醇酸树脂为天然植物油经高温反应制备得到；The high-solid low-VOC protective coating according to claim 1, wherein the high-solid low-viscosity alkyd resin is prepared from natural vegetable oil through high temperature reaction;
    所述高温反应的温度为180～250℃，时间为7～11h。The temperature of the high-temperature reaction is 180-250° C., and the time is 7-11 h.
  3. 根据权利要求2所述的高固体份低VOC防护涂料，其特征在于，完成所述高温反应后还包括加入二乙二醇丁醚和/或二乙二醇甲醚溶剂调整所得树脂的粘度。The high-solid low-VOC protective coating according to claim 2, characterized in that, after completing the high-temperature reaction, it further comprises adding diethylene glycol butyl ether and/or diethylene glycol methyl ether solvent to adjust the viscosity of the obtained resin.
  4. 根据权利要求2所述的高固体份低VOC防护涂料，其特征在于，所述天然植物油包括大豆油、亚麻油和棉籽油中的一种或几种。The high-solid low-VOC protective coating according to claim 2, wherein the natural vegetable oil comprises one or more of soybean oil, linseed oil and cottonseed oil.
  5. 根据权利要求1～4任意一项所述的高固体份低VOC防护涂料，其特征在于，所述高固低黏醇酸树脂在105℃烘烤1h的固含量为70±2％，在25℃的粘度为200～250s。The high-solid low-VOC protective coating according to any one of claims 1 to 4, wherein the solid content of the high-solid low-viscosity alkyd resin baked at 105° C. for 1 h is 70±2%, and the solid content is 70±2% at 25°C. The viscosity in °C is 200 to 250 s.
  6. 根据权利要求1所述的高固体份低VOC防护涂料，其特征在于，还包含15～20份的钛白粉，所述钛白粉为金红石型钛白粉，粒径为10～100nm。The high-solid low-VOC protective coating according to claim 1, further comprising 15-20 parts of titanium dioxide, wherein the titanium dioxide is rutile type titanium dioxide with a particle size of 10-100 nm.
  7. 根据权利要求6所述的高固体份低VOC防护涂料，其特征在于，所述重质碳酸钙的粒径为1100～1300目。The high-solid low-VOC protective coating according to claim 6, wherein the particle size of the heavy calcium carbonate is 1100-1300 mesh.
  8. 根据权利要求7所述的高固体份低VOC防护涂料，其特征在于，所述醇醚类溶剂包括二乙二醇甲醚、二乙二醇乙醚、二乙二醇丁醚、二丙二醇甲醚、二丙二醇丁醚、二甘醇乙醚和三丙二醇甲醚中的一种或几种。The high-solid low-VOC protective coating according to claim 7, wherein the alcohol ether solvent comprises diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, and dipropylene glycol methyl ether , one or more of dipropylene glycol butyl ether, diethylene glycol ethyl ether and tripropylene glycol methyl ether.
  9. 根据权利要求1或2或7或8所述的高固体份低VOC防护涂料，其特征在于，所述润湿剂为硅油；所述分散剂包括磷酸酯类分散剂；所述催干剂包括金属氧化物、金属盐和稀土催干剂中的一种或几种；所述防结皮剂为甲乙酮肟。The high-solid low-VOC protective coating according to claim 1 or 2 or 7 or 8, wherein the wetting agent is silicone oil; the dispersing agent includes a phosphate ester dispersing agent; the drier includes One or more of metal oxides, metal salts and rare earth driers; the anti-skinning agent is methyl ethyl ketoxime.
  10. 根据权利要求9所述的高固体份低VOC防护涂料，其特征在于，所述金属氧化物和金属盐中的金属独立地包括钴、锰、铁、锌或钙；所述稀土催干剂中的稀土元素包括铈、镧、钇中的一种或几种。The high-solid low-VOC protective coating according to claim 9, wherein the metal in the metal oxide and metal salt independently comprises cobalt, manganese, iron, zinc or calcium; in the rare earth drier The rare earth elements include one or more of cerium, lanthanum and yttrium.
  11. 根据权利要求1所述的高固体份低VOC防护涂料，其特征在于，所述涂料在25℃条件下的粘度为190～210s。The high-solid low-VOC protective coating according to claim 1, wherein the viscosity of the coating at 25°C is 190-210s.
  12. 权利要求1～11任一项所述高固体份低VOC防护涂料的制备方法，其特征在于，包括以下步骤：The preparation method of the high-solid low-VOC protective coating according to any one of claims 1 to 11, characterized in that, comprising the following steps:
    将部分醇醚类溶剂、部分高固低黏醇酸树脂以及剩余组分进行混合后研磨，得到浆料；所述剩余组分为除了催干剂、防结皮剂、醇醚类溶剂、高固低黏醇酸树脂之外的所有组分；Part of the alcohol ether solvent, part of the high-solid and low-viscosity alkyd resin and the remaining components are mixed and then ground to obtain a slurry; All components other than solid low viscosity alkyd resin;
    将所述浆料、剩余高固低黏醇酸树脂、催干剂、剩余醇醚类溶剂和防结皮剂混合，得到防护涂料。The slurry, the remaining high-solid and low-viscosity alkyd resin, the drier, the remaining alcohol ether solvent and the anti-skinning agent are mixed to obtain a protective coating.
  13. 根据权利要求12所述的高固体份低VOC防护涂料的制备方法，其特征在于，所述部分醇醚类溶剂占醇醚类溶剂总质量的75～85％；The method for preparing a high-solid low-VOC protective coating according to claim 12, wherein part of the alcohol ether solvent accounts for 75-85% of the total mass of the alcohol ether solvent;
    所述部分高固低黏醇酸树脂占高固低黏醇酸树脂总质量的65～75％；所述浆料细度≤40μm。The part of the high-solid and low-viscosity alkyd resin accounts for 65-75% of the total mass of the high-solid and low-viscosity alkyd resin; the fineness of the slurry is less than or equal to 40 μm.
  14. 根据权利要求12所述的高固体份低VOC防护涂料的制备方法，其特征在于，所述将部分醇醚类溶剂、部分高固低黏醇酸树脂以及剩余组分进行混合时，所述混合的速度为80～1000rpm。The method for preparing a high-solids and low-VOC protective coating according to claim 12, wherein when mixing part of the alcohol ether solvent, part of the high-solids and low-viscosity alkyd resin and the remaining components, the mixing The speed is 80 ~ 1000rpm.
  15. 权利要求1～11任一项所述的高固体份低VOC防护涂料或权利要求12～14任一项所述制备方法制备得到的高固体份低VOC防护涂料在工业防腐中的应用。Application of the high-solids low-VOC protective coating according to any one of claims 1 to 11 or the high-solids low-VOC protective coating prepared by the preparation method according to any one of claims 12 to 14 in industrial anticorrosion.
  16. 根据权利要求15所述的应用，其特征在于，所述工业防腐为钢结构防护。The application according to claim 15, wherein the industrial anticorrosion is steel structure protection.
  17. 一种高固低黏醇酸树脂的制备方法，包括以下步骤：A preparation method of high-solid low-viscosity alkyd resin, comprising the following steps:
    天然植物油经高温反应，制备得到高固低黏醇酸树脂；Natural vegetable oil is reacted at high temperature to prepare high solid and low viscosity alkyd resin;
    所述高温反应的温度为180～250℃，时间为7～11h。The temperature of the high-temperature reaction is 180-250° C., and the time is 7-11 h.
  18. 根据权利要求17所述的制备方法，其特征在于，完成所述高温反应后还包括加入二乙二醇丁醚和/或二乙二醇甲醚溶剂调整所得树脂的粘度。The preparation method according to claim 17, characterized in that, after completing the high temperature reaction, it further comprises adding diethylene glycol butyl ether and/or diethylene glycol methyl ether solvent to adjust the viscosity of the obtained resin.
  19. 根据权利要求17或18所述的制备方法，其特征在于，所述天然植物油包括大豆油、亚麻油和棉籽油中的一种或几种。The preparation method according to claim 17 or 18, wherein the natural vegetable oil comprises one or more of soybean oil, linseed oil and cottonseed oil.
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